Thermal decomposition of polychloroprene was studied under inert and oxidative atmospheres at temperatures of 500 and 850 degrees C in a horizontal quartz tubular laboratory reactor in order to determine the products generated. More than two hundred compounds, mainly aromatic hydrocarbons, were identified and quantified, with special focus on chlorinated aromatic compounds, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), chlorobenzenes (CBzs) and chlorophenols (CPhs). The results showed that pyrolysis of polychloroprene at high temperatures leaded to the formation of many aromatic hydrocarbons in high yields. In addition, the yields of total PCDD/Fs in the combustion experiment at 850 degrees C were more than three hundred times higher than those from pyrolysis at the same temperature. Results were also compared with those obtained in a previous work for polyvinyl chloride under similar operating conditions.